Development inhibitor yielding compound for silver halide photography

ABSTRACT

A light-sensitive silver halide photographic material is developed in the presence of a development inhibitor-yielding compound having the formula   wherein X is halogen COOR2 or, -O-Z, where Z is an alkyl group, aryl group, heterocyclic ring residue, acyl group, or -SO2-R3 (R3 is an alkyl group, aryl group or heterocyclic ring residue) and R2 is an alkyl group; and R is   where each of R1 is an aliphatic group or aryl group or two of the R1 groups may, together with the adjacent nitrogen atom, for a heterocyclic ring residue, and Y is a group which, when the thioether linkage has been split, forms, together with the sulfur atom, a compound having a development-inhibiting action.

United States Patent 1191 Fujiwhara et al.

[ Dec. 23, 1975 1 1 DEVELOPMENT INHIBITOR YIELDING COMPOUND FOR SILVER HALIDE PHOTOGRAPHY [75] Inventors: Mitsuto Fujiwhara; Takaya Endo;

Ryosuke Satoh; Toyoaki Masukawa; Takahiro Uozumi, all of Hino, Japan [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 22 Filed: Dec. 14, 1973 211 Appl. No.: 424,831

[30] Foreign Application Priority Data Primary ExaminerDavid Klein Assistant Examiner-Judson R. Hightower Attorney, Agent, or Firm-I-laseltine, Lake & Waters [57] ABSTRACT A light-sensitive silver halide photographic material is developed in the presence of a development inhibitoryielding compound having the formula wherein X is halogen COOR or, -OZ, where Z is an alkyl group, aryl group, heterocyclic ring residue, acyl group, or SO -R (R is an alkyl group, aryl group or heterocyclic ring residue) and R is an alkyl group; and R is where each of R is an aliphatic group or aryl group or two of the R groups may, together with the adjacent nitrogen atom, for a heterocyclic ring residue, and Y is a group which, when the thioether linkage has been split, forms, together with the sulfur atom, a compound having a development-inhibiting action.

9 Claims, N0 Drawings DEVELOPMENT INHIBITOR YIELDING COMPOUND FOR SILVER HALIDE PHOTOGRAPHY This invention relates to a development inhibitor yielding compound for silver halide photography. It has heretofore been well known to incorporate into a lightsensitive silver halide photographic material a compound capable of yielding a development inhibitor, depending on the density of image at the time of development of the photographic material (the said compound will be referred to as development inhibitoryielding compound, hereinafter). The said compound is, in general, of such a type that it reacts with the oxidation product of a color developer to yield a development inhibitor. Typical of such a compound is the so-called DIR coupler that is prepared by introducing into the coupling position of a coupler a group capable of forming a compound showing a development-inhibiting effect when it is released from the coupling position. This coupler has such properties that when coupled with the oxidation product of a color developing agent, it forms a dye and, on the other hand, yields a development inhibitor.

A development inhibitor-yielding compound is used, in general, for such purposes as mentioned below.

The compound has the characteristic that it yields a development inhibitor in correspondence to the density of image at the time of development. In case the thus yielded development inhibitor is present in the emulsion layer of the photographic material, the development of said layer is inhibited in relation to the image density, so that there may be expected the so-called intra-image effects such as control of image tone, fine graininess of image, and improvement in sharpness of image. On the other hand, in case the said development inhibitor has diffused into another layer, there may be expected, in the case of a color photographic material, such two image effects as the so-called masking action of inhibiting the development of said other layer in correspondence to the image density of the original layer, which is the diffusion source, and the so-called inter-image effect of inhibiting the development clue to monochromatic exposure or the like, of said other layer to improve the hue of the resulting image.

While various development inhibitor-yielding compounds have been known hitherto, all these compounds are not satisfactory for the above-mentioned expectations. For example, in the case of a development inhibitor-yielding compound which forms a dye at the time of color development, the resulting image becomes turbid unless the dye is carefully selected. If the dye is properly selected, it sometimes happens that a desired inhibiting effect cannot be obtained or it is not at all suitable for certain kinds of photographic material. On the other hand, a development inhibitor-yielding compound which forms no dye is low in reactivity with the oxidation product of a color developing agent, and hence is required to be used in a large amount. This results in such disadvantages that the photographic material is deteriorated in photographic properties (e.g. speed) and in stability, and that no sufficient effect can be attained of the compound is used in a small amount.

In the present invention, a novel development inhibitor-yielding compound is used, whereby the abovementioned disadvantages are overcome, and prominent wherein X is halogen COOR or, OZ, where Z is an alkyl group, aryl group, heterocyclic ring residue, acyl group, or SO R (R is an alkyl group, aryl group or heterocyclic ring residue) and R is an alkyl group; and R is or -SY, where each of R is an aliphatic group or aryl group, or two of R groups may, together with an adjacent nitrogen atom, form a heterocyclic ring residue, and Y is a group which, when the sulfur atom of the thioether linkage has been released, forms together with the sulfur atom, a compound having a development-inhibiting effect.

The development inhibitor-yielding compound used in the present invention forms a colorless compound even when reacted with the oxidation product of the color-devoloping agent. Since the thus formed colorless compound does not constitute any part of'the resulting image, the compound used in the present invention has the advantage that it can be applied singly, without using other compounds different in structure,

, to any layers or any photographic materials regardless of their kind. Further, the compound used in the present invention has an extremely high reactivity with the oxidation product of a color-developing agent, and hence has the advantage that excellent intra-image and inter-image effects can be attained even when the compound is used in a small amount. Moreover, the compound has the advantage that it can be selected from various development inhibitor-yielding compounds of the aforesaid general formula which may be used as photographic material and, in extreme cases, it can be incorporated into only one layer to act on all layers.

' Further, by adjusting the diffusibility of the develop- N-N ment inhibitor in the incorporated layer, it is possible to l no L form a gradient of the activity of the inhibitor in other 12P25 CO S N -N layers. The diffusible compound can be incorporated also into a color developer. On the other hand, the

non-diffusible compound is useful in the case where the intra-image and inter-image effects are desired to be imparted to a specific layer. In case a certain tendency is desired to be imparted to a layer, for example, the said compound may be used so as to vary the concentration of component constituting the said layer.

Typical examples of the compound used in the pres- CO cH S l Er ent invention are compounds of the aforesaid general formula, in which the alkyl group represented by Z is 1\I N preferably an alkyl group having I to 5 carbon atoms, 15

and the acyl group represented by Z is desirably 1] COR where R is preferably an alkyl or aryl group. The heterocyclic ring residue represented by any of Z and R is preferably a 5- or 6-membered heter- N-N ocyclic ring residue such as pyridine, furan or thio- (5) H phene, and the aliphatic group represented by R, i

which is a substituted or non-substituted group, is pref- )CH erably a saturated or olefinically unsaturated aliphatic 5 group having up to 18 carbon atoms. The heterocyclic ring residue represented by R is a 5- or 6-membered heterocyclic group, which may have one or more of N N such different atoms as N, O and S and may have a condensed benzene or naphthalene ring. In case there are two or more groups represented by R,, the said I groups may be different groups. The nitrogemcontain- 0 ing heterocyclic ring, which is formed by the combination of two groups represented by R in such a group as J SO N(R for example, is preferably a 5- to 6-membered ring. Typical examples of said ring are piperi- I dine, pyrrolidine and morpholine rings. The aryl groups represented by Z, R;,, R and R are typically phenyl (5) (3OJQH S and naphthyl groups, and may have been substituted by ,1

halogens, hydroxy groups, alkoxy groups or alkyl groups. The alkyl groups represented by Z, R, and R, l

are preferably those having up to 18 carbon atoms, and i maybe substituted by halogens, hydroxy groups or phenyl groups. On the other hand, Y in the formula is 5 a group which, when the sulfur atom of the thioether linkage has been released, fomis, together with the N-N ll sulfur atom, an allyl-mercapto compound, a heterocyclic compound, a compound of the thioglycolic acid COH OCOCH series, or cysteine, glutathione or the like compound 5 T T having a development-inhibiting action. Typical exam- COOC.,H ples of the mercapto compound represented by Y in- L 5 clude mercaptotetrazole type compounds, particularly 1-phenyl-2-mercaptotetrazole, l-nitrophenyl-S-mercaptotetrazole and l-naphthyl-S-mercaptotetrazole,

mercaptothiazole type compounds, particularly 2-mer- T T captobenzothiazole and mercaptonaphthothiazole, mercaptooxadiazole type compounds, mercaptopiperi- ('7) C H CO-CH S dine type compounds, mercaptothiadiazole type compounds, particularly Z-mercaptothiadiazolotriazine, 5 mercaptotriazine type compounds, mercaptotriazole type compounds, and mercaptobenzene type com- Q pounds, particularly l-mercapto-Z-benzoic acid, l-

mercapto-2-nitrobenzene and l-mercapto-3-heptadecanoyl-aminobenzene. Further, an alkyl group or a carbocyclic residue is also preferable as Y. Typical examples of the carbocylic residue are phenyl and the (8) l l 29 like aryl groups, and cycloalkyl and the like alicyclic N-N groups.

Concrete examples of compounds having the aforesaid general formula are as shown below.

NN o 9 Procedures for synthesizing typical compounds among those mentioned above are set forth below, and the other compounds can be synthesized according to these synthesis procedures.

SYNTHESIS EXAMPLE 1 Synthesis of compound (2) A mixture comprising 31 g. of w-chloroacetophenone and 40 g. of the sodium salt-of l-phenyl-S-mercaptotetrazole was heated in 400 cc. of acetone under reflux for minutes. After removing the sodium salt by filtration, the filtrate was concentrated under reduced pressure, and the residue was recrystallized from benzene to form w-( l-phenyl-5-tetrazolylthio) acetophenone. Into a solution of 30 g. of the thus formed acetophenone in 300 cc. of chloroform was dropped with stirring at 50 to 60C. a solution of 8 g. of bromine in 50 cc. of chloroform. After the dropping, the mixed chloroform solution was stirred at said temperature for 1 hour, washed with an aqueous dilute alkali carbonate solution, sufficiently washed with water, and then dried over anhydrous sodium sulfate. Subsequently, the chloroform was removed by distillation under reduced pressure, and the residue was recrystallized from benzene to obtain the compound (2), mp. 70-75C.

In same manner as above, the compounds (8), (10), (ll), (16), (20) and (21) were also synthesized by bromination.

SYNTHESIS EXAMPLE 2 Synthesis of compound (I) To a solution of 18.6 g. of n-dodecylbenzene and 100 g. of chloroacetyl chloride in 300 cc. of carbon disulfide was gradually added over a period of about minutes 10.5 g. of aluminum chloride with stirring at room temperature. Subsequently, the solution was refluxed for 30 minutes, and then the carbon disulflde was removed by distillation under reduced pressure. To the residue were added 600 g. of ice, 300 cc. of water and 60 cc. of concentrated: hydrochloric acid, and the resulting mixture was sufficiently stirred. Thereafter, the mixture was extracted with chloroform, thoroughly washed with water and dried, and then the chloroform was removed by distillation. The residue was recrystallized from a mixed solvent comprising methanol and acetonitrile to form pn-dodecyl-w chloroacetophe none. i

Subsequently, a mixture comprising 96 g. of the thus formed chloroacetophenone and g. of the sodium salt of 1-phenyl 5-mercaptotetrazole was refluxed for 30 minutes in 300 cc. of anhydrous acetone, and then subjected to filtration to remove sodium chloride. The filtrate was'concentrated, and the residue was recrystallized from a mixed solvent comprising methanol and acetonitrile to obtain p-n-dodecyl-w-( l-phenyl-S-tetrazolythio )acetophenone.

Into a solution of 45 g. of the thus obtained acetophenone in 800 cc. of chloroform was dropped with stirring at 0 to 5C. 15 g. of sulfuryl chloride. After the dropping, the stirring was continued at said temperature for 1 hour, and then the chloroform was removed by distillation under reduced pressure to synthesize compound (1) in the form of an oil.

SYNTHESIS EXAMPLE 3 A mixture comprising g.of compound 2) and l l g. of sodium methylate was refluxed for 1 hour in anhydrous acetone, and then'sodium bromide was removed. The residue was recrystallized from methanol to obtain compound (3), mp. 5055C.

In the same manner as above, except that the sodium methylate was replaced by a sodium salt having a corresponding substituent, compounds (4) and. (5) were obtained.

SYNTHESIS EXAMPLE 4 A mixture comprising.l9.5 g. of ethyl chloromalonate and 20 g. of the sodium salt of l-phenyl- 5-mercaptotetrazole was refluxed in' acetone. After removing sodium chloride, the solvent was removed by distillation to obtain compound (6) in the form of an oil.

In order to confirm the aforesaid compounds synthesized in such a manner as mentioned above, each compound was subjected to elementary analysis to measure the sulfur content thereof. The results obtained were as shown in the following table:

Elementary analysis (S) 7c Compound The compounds of the aforesaid general formula, which are synthesized in the above-mentioned manner, are usable in various silver halide photographic materials such as black-white, color and pseudo-color photographic materials, and applicable to silver halide photographic materials of various uses, such as ordinary black-white, printing black-white, X-ray, electron-ray, high resolution black-white, ordinary color, color X-ray and diffusion transfer type color photographic materials. The silver halides used in this case are silver chloride, silver bromide, silver iodide, and mixed silver halides, e.g. silver chlorobromide, silver iodobromide and silver chloroiodobromide. These may have been prepared according to any processes adopted for preparation of the so-called conversion emulsions or Lippmanns emulsions. The kind, grain size, content and mixing ratio of the silver halides vary depending on the nature of the photographic materials. In the case of relatively low speed photographic materials, the silver halides are composed mainly of silver chloride, while in the case of relatively high speed photographic materials, the content of silver chloride is low. For use in photographic materials of the direct positive type, the silver halides are fogged either optically or chemically. Further, the silver halides may be chemically sensitized with one or more of such sensitizers as active gelatin, sulfur sensitizers, e.g. allylthiocarbamide, thiourea and cystine, selenium sensitizers, and noble metal sensitizers including gold sensitizers, e.g. potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate and 2-aurosulfobenzothiazole metachloride, and ruthenium, rhodium, palladium and iridium sensitizers, e. g. ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which have been known to act as sensitizers or antifoggants depending on the amounts thereof.

The silver halides may be directly applied, in a binder-free form, onto a support by vacuum evaporation or the like. Alternatively, the silver halides may be brought to the form of the so-called silver halide emulsions by dispersing them in a binder comprising one or more of gelatin and the like colloidal substances, e.g. colloidal albumin cellulose derivatives, and polyvinyl and the like synthetic resins, and applied onto a support, if necessary through sub layer, inter layer, etc. The silver halide emulsions may be optically sensitized with, for example, cyanine or merocyanine dyes. In a color photographic material, for example, there are used three kinds of silver halide emulsions which are different from each other in sensitive wave-length region. Furthermore, the silver halide emulsions may be stabilized with triazoles, azaindenes, quaternary benzothiazolium compounds, or zinc or cadmium compounds, and may contain sensitizing compounds of the quaternary ammonium or polyethylene glycol type. The emulsions may further contain suitable gelatin stabilizers including glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylenebis-glycolic acid, bisethoxydiethyleneglycol succinate, acid amides of the acrylic acid type, and latexes; gelatin hardeners including formaldehyde, halogen-substituted fatty acids such as mucobromic acid, compounds having acid anhydride groups, dicarboxylic acid chlorides, biesters of methanesulfonic acid, and sodium bisulfite derivatives of dialdehydes whose aldehyde groups are separated by 2 to 3 carbon atoms; extenders such as saponin; coating aids such as sulfosuccinates; and the like various photographic additives. Particularly in the case of color photographic materials, the emulsions contain couplers, e.g. S-pyrazolone type, magenta couplers, naphthol or phenol type cyan couplers, and yellow couplers having active methylene groups interposed between two carbonyls, which may be the so-called 2-equivalent or 4-equivalent couplers, and may contain the so-called masking couplers which have, for example, arylazo groups in the coupling positions. The said masking couplers are preferably used in combination with the so-called colorless couplers, which are colorless before color development. The emulsions may contain dispersing agents for the couplers used in the above case, e.g. coupler solvents for the so-called protect type couplers. In order to enhance the photographic properties, the emulsions may further contain, in combination with various couplers, the so-called competing couplers which can form leuco-dyes.

For use in color photographic materials for diffusion transfer, on the other hand, the emulsions may contain, in place of the couplers, dye developers or coupler developers. The dye developers are compounds having both the functions of dyes and the functions of developers which are prepared by introducing hydroquinone or aromatic primary amino color developing agents into dyes, while the coupler developers are compounds having both the functions of couplers and the functions of developers which are prepared by introducing hydroquinone or the like into the coupling positions or other portions of the aforesaid couplers. In the case of color photographic materials for use in the silver dye bleaching method, the emulsions may contain dyes and, if necessary, ultraviolet absorbers, brighteners,

etc.

Such silver halide emulsion is applied onto a support, if necessary through sub layer, inter layer, etc., to prepare a light-sensitive silver halide photographic material. The support used in this case includes paper, laminated paper, glass, and cellulose acetate, cellulose nitrate, polyester, polyamide and polyethylene films and sheets, and is properly selected according to the intended use of the photographic material. Fundamentally, a photographic material is composed of a support and a photosensitive layer (silver halide-deposited layer or emulsion layer). As mentioned previously, however, the photographic material may have, depending on the intended use thereof, a sub layer, inter layer, filter layer, anti-curling layer, protective layer, etc. which have properly combined with each other. Further, the photosensitive layer itself may be composed of layers of emulsion varying in speed in the same or different wave-length region. These layers may contain various photographic additives, e.g. those incorporated into the aforesaid emulsions. Further, each layer may contain different additives, e.g. the filter layer may contain a filter dye, and the protective layer a film property-improving agent and an antistatic agent. As another embodiment, a diffusion transfer photographic material, for example, may have an inter layer contain- 1 1 ing a physical development nucleus.

The thus prepared silver halide photographic material is developed in the presence ofa compound having the aforesaid general formula to show such excellent photographic properties as mentioned previously. As another mode of practice, however, there is the procedure whereby the photographic material is previously incorporated with the said compound and is then subjected to development. In this case, the compound of the diffusible type may be incorporated into any layers of the photographic material, e.g. into one or more of the emulsion layer, inter layer, protective layer, etc., and the compound of the non-diffusible type is desirably incorporated into the emulsion layer, or into one or more layers adjacent thereto.

In preparing a photographic material incorporated with the said compound, the compound is added to a coating liquid for forming a layer of the photographic material. In this case, the compound may be used in any form. That is, the diffusible compound may be used in the form of a solution, e.g. an aqueous alkali solution, while the non-diffusible compound may be used in the form of an emulsion, e.g. an emulsion in the aforesaid coupler solvent. The coupler solvent is, in general, a water-immiscible high boiling organic solvent such as di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate, tri-o-cresyl phosphate or monodiphenyI-p-tbutylphenyl phosphate, or a mixture thereof with a low boiling solvent such as methyl isobutyl ketone, ,B-ethoxyethyl acetate, methoxytriglycol acetate, acetone, methylacetone, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, ethyl acetate, isopropyl acetate or chloroform. The low boiling organic solvent may be used in place of the high boiling organic solvent. The above-mentioned organic solvents may be used either singly or in the form of a mixture of 2 or more members.

According to another embodiment of the present invention, a diffusion transfer photographic material, for example, is developed in close contact with other photographic material, e.g. an image-receiving material. In this case, a compound of the aforesaid general formula may have been incorporated into said other photographic material. The compound used in this case is desirably of the diffusible type. However, the non-diffusible compound may also be used in the case where the image-receiving material is of such a type that silver halide particles on the physical development nucleus are to be adhered to the image-receiving layer (e.g. gelatin layer or polyvinyl resin layer) on the support.

According to another embodiment of the present invention, a compound of the aforesaid general formula is incorporated into a photographic material, or other photographic material such as an image-receiving material. In this case, the compound may be protected, depending on the kind of substituents thereof, with a carrier such as a mordant, and confined in a specific layer until the compound is required. For example, a compound having anion groups may be protected with amino groups in a certain mordant, and liberated at the time of development.

According to another embodiment of the present invention, a compound of the aforesaid general formula may be incorporated into a developer or a pretreating solution for the developer. Examples of said developer and pre-treating solution are black-white developers, color developers, e.g. ordinary color developers for the color films of the couplerincorporated type and the non-incorporated type, one or both of first and second developers in the case of reversal development, ordinary black-white developers and X-ray developers, and pre-treating solutions such as pre-hardening solutions. The compound used in the above case is desirably a diffusible compound, in general. It is also possible that a carrier is previously incorporated into a specific layer of photographic material to emphasize the effect of said layer. In the above case, the developer preferably contains an aromatic primary amino color developing agent.

In the present invention, the compounds of the aforesaid general formula are used in such various modes as mentioned above. All the compounds can give more excellent image effects than in the case where the conventional development inhibitor-yielding compounds are used. The effects are particularly marked when the compounds are incorporated into photographic materials. The amount of the compound used in the present invention varies depending on the application procedure, the intended use and the desired effect, but is preferably in the range from 0.1 to 10 g. per kg. of the emulsion. In case the compound is used in an amount equal to that of the conventional development inhibitor-yielding compound, the image effects become far greater than those attained by the conventional compound. For the attainment of the same-image effects as those attained by the conventional 1 compound, the compound may be used in an extremely small amount.

The composition of a developer, which has been incorporated with the compound of the aforesaid general formula, is as follows:

Color developer for color films of the coupler-nonincorporated type:

Color developing agent 2-8 g.

Sodium sulfite (anhydrous) l-6 g.

Sodium carbonate (monohydrate) 40-100 g. Potassium bromide 0.5-2 g. Coupler 0.0020.0I mole Compound of the aforesaid formula I.05.0 g. Water to make 1 liter Color developer for color films of the coupler-incorporated type:

The same composition as above, except that the coupler is not used.

According to the intended uses, the above-mentioned developers are controlled in pH and further incorporated with various other photographic additives.

Concrete compositions of the said developers are as follows:

Color developer for color films of the coupler-nonincorporated type:

N-Ethyl-N-B-methanesulfonamidoethyl-3-methyl-4- aminoaniline Sodium sulfite Benzyl alcohol Sodium Carbonate Potassium bromide Coupler Compound of the aforesaid formula Water to make Color developer for color films of the coupler-incorporated type:

N-Ethyl-NB-methancsulfonamidoethyl-3-methyl-4- 5.0 g aminoanilinc sulfate Sodium sulfitc (anhydrous) 2.0 g. Benzyl alcohol 3.8 g Sodium carbonate (monohydrate) 50 g. Potassium bromide l.0 g. Potassium hydroxide 0.55 g Compound of the aforesaid formula 2.5 g. Water to make I liter tion. For example, a photographic material having a layer incorporated with a non-diffusible compound of the aforesaid general formula may be treated with a processing solution containing a diffusible compound of the aforesaid general formula.

A photographic material, which has been developed in the above-mentioned manner according to the present invention, is then subjected to an ordinary photographic treatment comprising a suitable combination of steps selected from, for example, stopping, stop-fixing, fixing, bleaching, bleach-fixing, stabilizing, water-washing and drying steps.

The present invention is illustrated in more detail below with reference to examples, but the modes of practice of the invention are not limited thereto.

EXAMPLE 1 Samples l and II were prepared in the following manner:

Sample I 2 Grams of compound (I) and 15 g. of a magenta coupler l-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tertamylphenoxy acetamide)benzamide]-5-pyrazolone were dissolved in a mixed solvent comprising cc. of

ethyl acetate and 15 cc. of dibutyl phthalate. The resulting solution was mixed with 20 ml. of a 10% aqueous solution of Alkanol B (produced and sold by Du Font) and 200 ml. of a 5% aqueous gelatin solution, and then subjected to a colloid mill to form a dispersion. This dispersion was added to 1 kg. of a green-sensitive silver iodobromide emulsion, which was then coated on a triacetate base and dried to prepare a sample l.

Sample II For comparison, a sample [I was prepared in the same manner as above, except that compound l) was not used.

Samples l and II were individually exposed through an optical wedge, developed with a developer of the composition shown below, and then subjected to ordinary bleach-fixing treatment. Developer composition:

N,N-Dimethyl p-phenylenediamine hydrochloride 2.0 g. Anhydrous sodium sulfite 2.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g. Water to make liter As the result, both of the samples formed images comprising a magenta dye. The two samples were identical in speed, but the y-value of sample II was 0.9 and that of the sample I was 0.5.

The grains constituting the magenta image of the sample II were considerably finer than in the case of sample 1.

EXAMPLE 2 Samples Ill and IV were prepared in the following manner:

Sample Ill 15 Grams of 2-[a-(2,4,-di-t-amylphenoxy)- butyramide]-4,6-dichloro-5-methylphenol was added to 1 kg. of a red-sensitive silver iodobromide emulsion, which was then coated on a triacetate base to form an emulsion layer. Subsequently, a green-sensitive silver halide emulsion containing 7 g. of compound (9) and 20 g. of 1-(2,4,6-trichlorophenyl)-3-{3-[a-(2,4-di-tamylphenoxy)acetamide1benzamide}-5-pyrazolone was coated on the above-mentioned emulsion layer, and then dried to prepare a sample lll.

Sample IV For comparison, a sample IV was prepared in the same manner as above, except that the green-sensitive emulsion contained only the magenta coupler and did not contain compound (9).

Samples Ill and IV were individually exposed through an optical wedge to red light and white light, developed with the same developer as in Example 1, and then subjected to ordinary bleach-fixing treatment.

As the result, the 'y-values of the cyan images formed by exposing sample III to red and white light were substantially identical with each other, whereas the y-value of the cyan image formed by exposing sample IV to white light was obviously smaller than that of the cyan image formed by exposing said sample to red light. From this, it is understood that in sample III, a development inhibitor, which had been released from the compound (9) by exposing sample to white light, diffused into the lower red-sensitive layer, with the result that the development of the red-sensitive layer was inhibited to lowerthc 'y-value of the image.

EXAMPLE 3 To a solution of 0.8 g. of the disodium salt of l-phenyl-3-( 3 ,5 -di-sulfobenzamido )-4-( n-octadecyloxyphenylazo )-5-pyrazolone as a coupler in 40 cc. of water was added with stirring at room temperature 5 cc. of a [0% aqueous sodium hydroxide solution. The solution was mixed at ,40C. with cc. of a 10% aqueous gelatin solution, 8 cc. of a 5% aqueous Alkanol B solution, and 16cc. of a 7% saponin solution, and then adjusted to pH 6.8. To this solution was added 8 cc. of a silver iodobromide emulsion, which was then stirred for 2 minutes, allowed to stand at 40C. for 30 minutes, filtered and then coated on a triacetate base to form an emulsion layer on the base. Subsequently, the emulsion layer was fogged by exposing the layer for 30 seconds to a 40-watt electric lamp at a distance of 1.5 m. On the thus fogged emulsion layer was coated an emulsion prepared in the following manner:

A mixture comprising 0.8 g. of compound (9), 0.8 cc. of 2,4-di-n-amylphenol and 0.8 cc. of dimethylformamide was heated with stirring at 80C. to form a solution. This solution was mixed at 40C. with 20 cc. of a 10% aqueous gelatin solution and 2 cc. .of a 5% aqueous Alkanol B solution, and the resulting suspension was subjected 5 times to a colloid mill to form a dispersion. To this dispersion, including the residual dispersion that had been washed off from the mill by use of 8 cc. of water and 2 cc. of a 7% aqueous saponin solution, was added 10 cc. of a silver chlorobromide emulsion.

The thus prepared emulsion was stirred for 2 minutes, allowed to stand at 40C. for 30 minutes, and then coated on the aforesaid fogged emulsion layer to prepare a light-sensitive film.

On the other hand, a mixture comprising 25 cc. of a 10% gelatin solution and 0.5 g. of cetyl-trimethylam monium bromide was coated on a film to prepare an image-receiving film.

After exposure, the above-mentioned light-sensitive film was contacted with the image receiving layer of the image-receiving film, and then developed with a developer of the following composition:

Sodium carbonate 20.0 g Sodium hcxamctaphosphatc 2.0 g Bcnzyl alcohol 10.0 g 3-Acetamide-4-amino-N,N-

diethylaniline 2.0 g. Water to make I litcr With progress of the development, a development inhibitor was formed in the exposed portions. The inhibitor diffused into the lower fogged emulsion layer, and successfully inhibited the development of the corresponding portions. ln unexposed portions,where the lower fogged emulsion layer was not inhibited in development, the coupling of the developing agent with the coupler took place to form a soluble magenta dye. This magenta dye transferred image-wise to the imagereceiving layer containing the mordant to form a brilliant positive magenta image.

EXAMPLE 4 A sample was prepared by forming on a triacetate base the following layers in the order shown below (weight per 900 cm l. A red-sensitive silver iodobromide emulsion layer containing 440 mg. of gelatin and 174 mg. of silver halide. The emulsion layer additionally contained 26.3 mg. of l-hydroxy-4-(4-t-butylphenoxy)-4-phenylazo- 2-naphthanilide and 32.7 mg. of l-hydroxy-N-[oz-(2,4- di-t-amylphenoxy)butyl-Z-naphthamide] as couplers, and 7 mg. of the compound (23).

2. A gelatin inter-layer containing 83 mg. of gelatin and 5 mg. of dioctyl hydroquinone.

3. A green-sensitive silver iodobromide emulsion layer containing 400 mg. of gelatin and 243' mg. of silver halide. The emulsion layer additionally contained 24.5 mg. of l-(2,4,6-trichlorophenyl)-3-{3 [a-(2,4-dit-amylphenoxy)acetamide] benzamide}-4-(4-methox- 16 yphenylazo)-5-pyrazolone and 24.3 mg. of l-(2,4,6-trichlorophenyl )-3 3-[ a-( 2,4-di-t-amylphenoxy )acetamide] benzamide}-5-pyrazolone as c0uplers,-and 7 mg. of the compound (23). emulsion layer further contained 8.7 mg. of dioctyl hydroquinone as an anti-stain agent.

4. A gelatin inter-layer containing 83 mg. of gelatin and 5 mg. of dioctyl hydroquinone.

5. A blue-sensitive silver halide emulsion layer containing 200 mg. of gelatin and 62 mg. of silver halide. The emulsion layer additionally contained 102.5 mg. of N-(p-benzoylacetamidobenzenesulfonyl )-N-( a-phenylpropyl)-p-toluidine as a coupler and 2.3 mg. of dioctyl hydroquinone as an anti-stain agent. I

For comparison, a sample was prepared in the same manner as above, except that the red-sensitive and green-sensitive emulsion layers did not contain the compound (23).

The two samples were individually exposed through an optical wedge, and then developed at 24C. for 10 minutes with a developer of the following composition:

Anhydrous sodium sulfate 2.0 g. N-Ethyl-NB-methanesulfonamidoethyl-3-mcthyl-4-aminoaniline 5.0 g. sulfate Sodium carbonate 50.0 g. Sodium bromide 09 g. Sodium hydroxide 4.0 g. Sodium hexametaphosphate 0.5 g. Benzyl alcohol 4.0 ml. Pure water to make l liter After the development, the samples were subjected to ordinary bleach-fixing treatment.

The former sample according to the present invention which contained compound (23) had more excellent sharpness, and granularity and lessfog than the latter sample. I

. XA e Samples A and B were prepared the following manner:

SampleA.

7.2 Grams of compound l )-.and 15 g. 10f l?(.2,4,6.-trichlorophenyl )-3- {3-[( 2 ,4-di-t-amylphenoxy)acetamide] benzimide}-5-pyrazolone as a magenta coupler were dissolved in a mixed'so'l'v'ent comprising 30 cc. of ethyl acetate and 20 cc, o f:clibutyl,phthalate. The; re-

sulting solution was mixed with20 ml. of a lO%,aque-.

ous Alkanol B solution and 200ml. of a 5% aqueous gelatin solution, and then dispersed by means of a colloid mill to forrna dispersion. Thisdispersion was added to l kg. of agreen-sens itive silver iodobromide emulsion, which was then coated on a triacetate base and dried to prepare sample A.

Sample B 17 EXAMPLE 6 N-Ethyl-N-fi-methanesulfonamidoethyl-3-methyl-4-aminoaniline 5.0 g. sulfate Sodium sulfite (anhydrous) 2.0 g. Benzyl alcohol 3.8 g. Sodium carbonate (monohydrate) 50 g. Potassium bromide 1.0 g Potassium hydroxide 0.53 g Compound (24) 1.5 g. Water to make 1 lite For comparison, the above-mentioned color photo graphic film was treated in the same manner as above, except that the developer did not contain compound (24).

As the result, the image formed according to the present invention was far more excellent, due to the prominent image effects displayed by compound (24), in sharpness and granularity and more brilliant in hue than the image formed in the film treated in the absence of compound (24).

What we claim is:

1. A method for development of an imagewiseexposed light-sensitive silver halide photographic material which comprises subjecting the imagewise-exposed light-sensitive silver halide photographic material to development in the presence of a development inhibitor-yielding compound having the formula wherein X is halogen, COOR or OZ, where Z is an alkyl group, aryl group, heterocyclic ring residue, acyl group, or SO R R is an alkyl group, aryl group or heterocyclic ring residue and R is an alkyl group; and R is where each R, is an aliphatic group or an aryl group or two of the R, groups may, together with the adjacent nitrogen atom, form a heterocyclic ring residue, and Y is a group which, when the thioether linkage has been split, forms, together with the sulfur atom, a compound having a development-inhibiting action.

2. A light-sensitive silver halide photographic material containing a development inhibitor-yielding compound having the formula wherein X is halogen, COOR or OZ, where Z is an alkyl group, aryl group, heterocyclic ring residue, acyl group, or SO -R R is an alkyl group, aryl group or heterocyclic ring residue and R is an alkyl group; and R is where each R, is an aliphatic group or aryl group or two of the R, groups may, together with the adjacent nitrogen atom, form a heterocyclic ring residue, and Y is a group which, when the thioether linkage has been split, forms, together with the sulfur atom, a compound having a development-inhibiting action.

3. A photographic material according to claim 2 wherein Z is an alkyl group having 1 to 5 carbon atoms.

4. A photographic material according to claim 2 wherein Z is a COR, group in which R, is an alkyl or aryl group.

5. A photographic material according to claim 2 wherein Z is a heterocyclic ring residue selected from the group consisting of pyridine, furan and thiophene.

6. A photographic material according to claim 2 wherein R, is a saturated or olefinically unsaturated aliphatic group having from 1 to 18 carbon atoms.

7. A photographic material according to claim 2 wherein the heterocyclic ring residue formed by R, and the adjacent nitrogen atom is selected from the group consisting of piperidine, pyrrolidine and morpholine.

8. A photographic material according to claim 2 wherein the aryl groups are selected from the group consisting of phenyl and naphthyl groups optionally substituted by halogens, hydroxy groups, alkoxy groups or alkyl groups.

9. A photographic material according to claim 2 wherein the compound having a development-inhibiting action is selected from the group consisting of 1- phenyl-2-mercaptotetrazole, l-nitrophenyl-S-mercaptotetrazole, lnaphthyl-S-mercaptotetrazole, 2-mercaptobenzothiazole, mercaptonaphthothiazole, mercaptooxadiazoles, mercaptopiperidines, mercaptothiadiazoles, mercaptotriazines, mercaptotriazoles, lmercapto-Z-benzoic acid, 1mercapto-Z-nitrobenzene and 1mercapto-3heptadecanoylaminobenzene. 

1. A METHOD FOR DEVELOPMENT OF AN IMAGEWISE-EXPOSED LIGHT-SENSITIVE HALIDE PHOTOGRAPHIC MATERIAL WHICH COMPRISES SUBJECTING THE IMAGEWISE-EXPOSED LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL TO DEVELOPMENT IN THE PRESENCE OF A DEVELOPMENT INHIBITOR-YIELDING COMPOUND HAVING THE FORMULA
 2. A light-sensitive silver halide photographic material containing a development inhibitor-yielding compound having the formula
 3. A photographic material according to claim 2 wherein Z is an alkyl group having 1 to 5 carbon atoms.
 4. A photographic material according to claim 2 wherein Z is a -COR4 group in which R4 is an alkyl or aryl group.
 5. A photographic material according to claim 2 wherein Z is a heterocyclic ring residue selected from the group consisting of pyridine, furan and thiophene.
 6. A photographic material according to claim 2 wherein R1 is a saturated or olefinically unsaturated aliphatic group having from 1 to 18 carbon atoms.
 7. A photographic material according to claim 2 wherein the heterocyclic ring residue formed by R1 and the adjacent nitrogen atom is selected from the group consisting of piperidine, pyrrolidine and morpholine.
 8. A photographic material according to claim 2 wherein the aryl groups are selected from the group consisting of phenyl and naphthyl groups optionally substituted by halogens, hydroxy groups, alkoxy groups or alkyl groups.
 9. A photographic material according to claim 2 wherein the compound having a development-inhibiting action is selected from the group consisting of 1-phenyl-2-mercaptotetrazole, 1-nitrophenyl-5-mercaptotetrazole, 1-naphthyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, mercaptonaphthothiazole, mercaptooxadiazoles, mercaptopiperidines, mercaptothiadiazoles, mercaptotriazines, mercaptotriazoles, 1-mercapto-2-benzoic acid, 1-mercapto-2-nitrobenzene and 1-mercapto-3-heptadecanoyl-aminobenzene. 